CN1082030C - Fine Particles of petaloid porous hydroxyapatite and process for producing the same - Google Patents

Abstract

Provides hydroxyapatite particles with a Ca/P atomic ratio of 1.62 to 1.72 and a chemical formula of Ca ₅ (PO ₄ ) ₃ (OH), which have petal-like pores on the surface and inside, and particles with a specific particle size. Petal-shaped porous hydroxyapatite microparticles with diameter, pore size of specific particle size, specific surface area of specific range, static porosity of specific range and pressurized porosity of specific range. It has good dispersibility and is useful in the fields of carriers such as medicines, adsorbents, absorbents, sustained-release agents, filters, biomaterials, fillers such as plastics, and anti-blocking agents such as films.

Description

Petal-shaped porous hydroxyapatite microparticles and method for producing the same

technical field

The present invention relates to novel specific particle size, specific dispersibility, specific pore size and specific porosity, and the atomic ratio of Ca/P is 1.62 to 1.72, and the chemical formula is Ca ₅ (PO ₄ ) ₃ (OH) Petal-shaped porous hydroxyapatite microparticles and a method for producing the same. In addition, the production method provided by the present invention is an industrially easy production method of the petal-shaped porous hydroxyapatite microparticles of the present invention at low cost.

The petal-shaped porous hydroxyapatite microparticles of the present invention are used as catalyst carriers, pharmaceutical carriers, pesticide carriers, microbial carriers, organism carriers, peroxide carriers, plant growth agents, olefin absorbents, ultraviolet absorbents, adsorbents, slow-release Agents, liquid absorbents, ceramic raw materials, various carriers, filter agents, filter aids, molding aids, microbial culture, biological materials, desiccants, fragrances, other carriers or their raw materials, plastics, rubber, coatings, and inks · It is useful as a filler for sealing materials and papermaking, and as an anti-blocking agent for fibers and films. In addition, newer uses can be developed by combining the various uses described above.

Background technique

In the past, it has long been known that porous hydroxyapatite exists in living organisms. For example, is the main component of bones and teeth. Therefore, in recent years, various studies have been conducted to attract attention as a raw material for bioceramics. In addition, fine powder hydroxyapatite without a porous structure is industrially produced and sold as a raw material of the above-mentioned porous hydroxyapatite, a food additive (as tricalcium phosphate), a polymerization stabilizer, a catalyst, and the like. .

As porous hydroxyapatite, (1) spherical apatite, (2) apatite porous body, (3) calcium phosphate hollow body, (4) calcium phosphate compound granular body, (5) phosphoric acid Calcium-based porous bone filling materials, (6) spherical calcium phosphate-based porous bodies, and the like. The outline is described below.

(1) Examples of spherical apatite include "Spherical apatite, its production method, and a molded body with a porous structure" in JP-A-3-16906.

This article describes calcium phosphate having a Ca/P molar ratio of 1.4 to 1.8, and relates to spherical apatite having a specific gravity of 3.00 to 3.17, which is characterized by spherical shape and compactness, and high mechanical strength. However, because it is dense, it has the disadvantage of extremely low porosity.

The production method is to dry the slurry containing hydroxyapatite as the main component, then pulverize it, adjust the aggregated particles of the primary particles of the apatite, preferably adjust it into a spherical shape by spray drying, and make the aggregated aggregates of the primary particles of the apatite adjusted Melting in a flame above 1500°C to obtain spherical apatite.

In addition, the above-mentioned spherical apatite is mixed with a binder, press-molded, and then sintered in a flame at 1500°C or higher to obtain apatite with a porous structure, but the obtained porous body The porosity is extremely low as a numerical value of 28% in Examples, and it cannot be said to be a porous body with a high porosity.

(2) Examples of the porous apatite body include "Method for producing a porous apatite body" in JP-A-2-14311.

As claim 1 therein, it is described that "calcium carbonate powder is mixed with calcium hydrogen phosphate dihydrate or its anhydrate at a ratio of Ca/P molar ratio of 1.50 to 1.67, and water is added thereto to carry out hydration reaction. Manufacturing method of apatite porous body".

The obtained porous body is not a fine particle, and the whole is hardened by a hydration reaction, so it is not a porous body fine particle. Although the single-phase apatite hydrogel with a porosity of 71-76% was obtained in the examples, its chemical formula is Ca ₁₀ -z(HPO ₄ )(PO ₄ ) ₆ -z(OH) ₂ -z·nH ₂ O, where Z=0, contains the crystal water represented, not hydroxyapatite. By sintering the apatite hydraulic body at 1000-1350°C, hydroxyapatite represented by Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ is obtained, and the porosity corresponding to the porosity is lower than that before sintering. , The porosity of the hydroxyapatite obtained in Examples is an extremely low value of 45 to 50%. Although it is stated in the specification that the porosity can be controlled in a high range, there is no description about the porosity of hydroxyapatite higher than 45% to 50%, and there is no description about its production method.

In addition, in Examples 1 to 4 and any of the comparative examples, the hydration reaction was performed at 50°C or 80°C in the inside of the capped pyrex glass tube. The reaction formula recorded in the description shows that 1 mol of carbon dioxide is generated relative to 1 mol of calcium carbonate as a raw material, and due to the carbon dioxide generated in the reaction, a high pressure exceeding atmospheric pressure is formed inside the covered pyrex glass tube, and the hydration reaction It is a reaction method similar to an autoclave under pressure. In addition, there is no description about using specific calcium hydrogen phosphate dihydrate or specific calcium carbonate.

(3) Examples of the calcium phosphate hollow body include "calcium phosphate hollow body" in JP-A-63-198970.

This publication is about hollow spheres with openings, not about porous bodies, and the specific surface area described is obviously lower than 10m ² /g, but 1-6m ² /g.

As a manufacturing method, the method of mixing calcium phosphate and an organic foaming agent, foaming it, and firing at 900-1400 degreeC is described.

(4) Examples of calcium phosphate compound granules include "calcium phosphate compound granules" in JP-A-1-230412.

This publication is about granular bodies, not porous bodies. In addition, the described real surface area (specific surface area) is an extremely low value of 0.02 to 0.05 m ² /g.

As a production method, it is described that hydroxyapatite and an organic binder are used to produce granules by granulation, etc., and then the organic binder is eliminated by sintering, or instead of the organic binder, a non-aqueous solvent is used. A method for granulating, drying and sintering the binder of apatite sol. Removal of organic binders or non-aqueous solvents is essential.

(5) Examples of the calcium phosphate-based porous bone filling material include "calcium phosphate-based porous bone filling material" in JP-A-1-49501.

The porous bone filling material obtained in this gazette relates to a large porous body of several mm or more.

As a production method, it is described that after wet-mixing pyrolytic beads such as hydroxyapatite powder and polystyrene beads, and a foaming agent such as hydrogen peroxide, foaming and drying are carried out in a desiccator, and a specified The method of thermally decomposing and sintering the obtained dry body under the temperature rising condition of 900-1400°C.

(6) Examples of the spherical calcium phosphate porous body include "Method for producing spherical calcium phosphate porous body" in JP-A-4-44606.

It is described in this publication that the obtained spherical calcium phosphate-based porous body can have igagly-shaped (Y-shaped) or spherical pores, a specific surface area of 1 to 50 m ² /g, a particle diameter of 1 to 100 μm, and a pore diameter of 1 to 100 μm. 0.01 to 0.5 μm. Hydroxyapatite (hydroxyapatite) described in Examples has a specific surface area of 5 m ² /g and an extremely low surface area. Although it is also described that the particles are sintered at 1100°C, there may be a spherical shape with an enlarged pore diameter, but it is generally believed that the specific surface area becomes smaller after the pore diameter is heat-treated (sintered), so the specific surface area after heat treatment is estimated to be 5m ² /g or less. Regarding the spherical calcium phosphate-based porous body composed of β-tricalcium phosphate other than hydroxyapatite, there is only a description that its specific surface area is 10 m ² /g higher than that of the above-mentioned hydroxyapatite (hydroxyapatite) However, it cannot be said that a spherical calcium phosphate-based porous body composed of hydroxyapatite with a specific surface area of 50 m ² /g can be easily prepared.

As a production method, it is described that after adjusting 1 mol of water-soluble calcium salt, 1 to 1.2 mol of a calcium ion complexing agent, and 0.5 to 1 mol of water-soluble phosphate to a pH range of 5 to 11, hydrogen peroxide is added thereto to a concentration of 1 ~20% by weight, the method of generating by heating reaction at a temperature of 50-100°C and further heat treatment (sintering) at 900-1500°C. It is necessary to wash and remove reaction by-products (salts such as NaCl) and calcium ion complexing agents with water. Furthermore, it is presumed that the higher the specific surface area, the more difficult it is to separate these impurities, and the easier it is for impurities to remain.

The conventional manufacturing method of porous hydroxyapatite is mainly a method of aggregating well-known microparticles of hydroxyapatite such as flakes, needles, and spheres, and obtaining a porous body from interparticle distances and aggregated voids. The effect is large, and the obtained porous hydroxyapatite has to be limited by its disadvantages as described above. As a method of increasing the porosity, it is mainly a method of using a foaming agent, an organic sphere, and an organic binder at the same time. Since these foaming agents, organic spheres, and organic binders are originally not suitable for porous hydroxyapatite Therefore, it is necessary not only to remove them by a removal process such as sintering, but also to sinter the fine particles of hydroxyapatite as a raw material during sintering, resulting in a decrease in the specific surface area. When the additive is not removed by sintering or the like, the specific surface area and porosity decrease due to the adsorption of the additive compared to the case where no additive is added.

In the method of slurrying with a solvent alone, and then spray drying to prepare fine particles, the obtained particles are easily broken, and have the same disadvantages as the above-mentioned case of increasing the porosity, since the same binder is required.

Although there is also a method of obtaining porous hydroxyapatite by sintering or melting calcium phosphate particles other than hydroxyapatite instead of fine particles of hydroxyapatite as a raw material, the fine particles of the raw material are also sintered with each other, so As a result, the specific surface area decreases.

The methods for producing hydroxyapatite using conventional techniques are listed below. However, these methods are not related to methods for producing porous hydroxyapatite.

(7) As a report on a calcium phosphate-based compound having a high specific surface area, "a calcium phosphate-based sustained-release product" in JP-A-5-68442 is cited.

Although it is stated in claim 1: "A substrate composed of hydroxyapatite with a specific surface area of 100 to 250 m ² /g produced by the BET method is used to adsorb deodorants, fungicides, pesticides, fungicides, and insect repellants. Calcium phosphate-based slow-release body composed of desorbed substances of at least one composition", but there is no description about porous hydroxyapatite.

The method for producing hydroxyapatite described in Example 1 is a known method of adding a 40% concentrated phosphoric acid aqueous solution to a 10% calcium hydroxide aqueous suspension.

(8) A method of preparing by gradually adding phosphoric acid to an aqueous calcium hydroxide suspension.

The method in (7) above can be mentioned. This method has the advantage of not generating by-products other than calcium phosphate, and is excellent as a method for obtaining a mixture of hydroxyapatite and tricalcium phosphate. Generally, the hydroxyapatite particles obtained by this method are needle-shaped, flake-shaped and spherical ultrafine particles below 0.1 μm. Because the obtained ultrafine particles are not only poor in dehydration and filterability after the reaction (slow filtration rate), Moreover, because of poor dehydration and filterability, it is not easy to clean, and there are also disadvantages such as easy aggregation of dry powder. In addition, unreacted calcium hydroxide tends to remain, and since the remaining calcium hydroxide exhibits high alkalinity, it has disadvantages such as exerting a bad influence on adsorbed substances. As an improved method, for example, the following methods are reported, that is, the method of removing unreacted calcium hydroxide after the reaction is completed by washing with water and/or the method of heat treatment above the decomposition temperature of calcium hydroxide, preferably above 900° C., and the method of making hydrogen Calcium oxide and phosphoric acid are reacted, and wet grinding is performed using grinding media such as glass beads to improve reactivity.

(9) Many methods for improving the disadvantage in (8) above have been reported.

After the reaction is completed, a hydrothermal synthesis method in which heat treatment is carried out at a high temperature of 80° C. or higher for a long time or in a closed container (autoclave) for a long time; (preferably above 900°C) method of sintering synthesis by sintering reaction; method of grinding and pulverizing during reaction to improve reactivity, etc. Although hydroxyapatite can be obtained by these methods, it not only makes the process of obtaining hydroxyapatite quite complicated, but also reduces the specific surface area due to heat treatment, reduces the porosity due to sintering, and destroys the porosity due to grinding. Quality and other shortcomings.

(10) A method in which an insoluble or poorly soluble calcium salt and phosphate are hydrated in water to form an intermediate, and the intermediate is prepared by sintering and synthesizing.

A method of using calcium carbonate as the calcium salt and calcium hydrogenphosphate dihydrate as the phosphate is also reported. If the method in (2) above is mentioned, then there are the same disadvantages as above. In addition, a method of carrying out the reaction in water under stirring is also reported.

For example, "Method for producing hydroxyapatite" in JP-A-62-223010 is mentioned, but it does not describe examples of combining calcium carbonate and calcium hydrogen phosphate dihydrate and obtaining specific hydroxyapatite. In addition, although the "production method of hydroxyapatite containing carbonic acid" in Japanese Patent Publication No. 58-30244 can be mentioned, this method is characterized by using ammonium hydroxide in combination to obtain hydroxyapatite containing carbonic acid different from hydroxyapatite. Apatite method. In addition, it is recorded in Angew.Chem.internat.Edit./Vol.5(1996)/No.7 p669-670 that the salt slurry of calcite crystal calcium carbonate and calcium hydrogen phosphate dihydrate was prepared with KOH, and then passed into the refined The air, at 37 ° C, after a few days, carbonate-apatite was obtained as a product, that is, 5/4 [Ca(PO ₄ ) ₂ (HPO ₄ ) _0.4 (CO ₃ ) _0.6 ], in X-ray diffraction Middle is a diffraction feature similar to octacalcium phosphate (オクトカツウウムホスヘ一ト). This product is different from the hydroxyapatite of the present invention.

(11) As a report on hydroxyapatite with a high specific surface area, it is described in Journal of Colloid and Interface Science, Vol.55, No.2 (1976) p409-p414, starting Ca ²⁺ /PO ₄ ^3- = 1.71, the reaction itself was carried out at room temperature under a nitrogen atmosphere. After the reaction, while stirring, the precipitated amorphous calcium phosphate was contacted with the alkaline mother liquor for 4 days, and the product was centrifuged and passed through the Spectrapor membrane hose for Dialyzed, washed with distilled water, and dialyzed until the washing solution became neutral, and then freeze-dried to obtain hydroxyapatite with a specific surface area of 198 m ² /g measured by the BET method. This product is different from the petal-shaped porous hydroxyapatite of the present invention.

(12) As a report on hydroxyapatite with a high specific surface area, it is described in Inorganic Chemistrg (1982), Volume 21, No. 8 p3029-3035. A certain pH of 7.40, 8.25, 9.75, 10.00, through precipitation reaction, get non-stoichiometric amorphous and crystalline calcium phosphate. Here, removing all the calcium carbonate generated when obtaining a saturated solution of calcium hydroxide to minimize the calcium carbonate content in the system is not a method of producing hydroxyapatite from calcium carbonate and phosphoric acid as in the present invention. In addition, the produced calcium-deficient hydroxyapatite had a specific surface area of 163 m ² /g as measured by the BET method. However, as a pH adjustment method, because the mixing ratio of the phosphoric acid solution and the calcium hydroxide saturated solution is adjusted, the Ca/P of the generated powder is 1.40 to 1.58, and the high-purity hydroxyapatite like the present invention cannot be obtained.

(13) A method of preparing by mixing a solution of a water-soluble calcium salt and a water-soluble phosphate salt.

The above (6) is such an improved method, which has disadvantages of control of the reaction, removal of by-products, and the like.

(14) A method in which calcium methoxide and an organic phosphoric acid compound are subjected to a hydrolysis reaction in an organic solvent, and an intermediate amorphous calcium phosphate is prepared, chemically changed, sintered, or the like.

It has disadvantages such as the use of expensive raw materials, complicated process, instability of amorphous calcium phosphate, and problems in reproducibility.

(15) A dry synthesis method in which tricalcium phosphate and calcium salt are reacted at 900° C. or higher under a stream of water vapor.

Because it is sintered at high temperature, it has the disadvantages of low specific surface area and low porosity. There is also an improved method of adding excess calcium salt and washing with water to remove CaO produced by the excess calcium salt after the reaction is completed.

(16) As a combination of calcium carbonate and phosphoric acid, "the production method of hydroxyapatite" in JP-A-1-290513 can be cited, but this method is to react calcium carbonate and phosphoric acid, and Ca/P is 1.5 Tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) is used as an intermediate, and calcium hydroxide is added to this intermediate in a sealed container to produce hydroxyapatite whose Ca/P is 1.67, not from calcium carbonate and Method for producing hydroxyapatite from phosphoric acid.

Heretofore known methods for producing calcium phosphate with an atomic ratio of 0.5 to 1.5 from calcium carbonate and phosphoric acid include calcium dihydrogen phosphate with Ca/P=0.5, calcium hydrogen phosphate with Ca/P=1, and calcium hydrogen phosphate dibasic. Hydrate, tricalcium phosphate with Ca/P=1.5, etc.

In the conventional manufacturing methods of porous hydroxyapatite and hydroxyapatite, there is no report on porous hydroxyapatite microparticles satisfying simultaneously adjustable high porosity, high specific surface area and specific pore diameter and its Moreover, there is no report on the porous hydroxyapatite fine particles of a specific particle size that maintains excellent physical properties, is easy to process, and has good dispersibility.

Thus, porous hydroxyapatite microparticles satisfying both high porosity, high specific surface area and specific pore diameter and a method for producing the same are required. Furthermore, since this porous hydroxyapatite maintains excellent physical properties, is easy to process, and is fine particles of a specific particle size with good dispersibility, it is expected not only as a raw material for bioceramics but also for multipurpose applications. Such application fields include catalyst carriers, pharmaceutical carriers, pesticide carriers, microbial carriers, biological carriers, peroxide carriers, plant growth agents, olefin absorbers, ultraviolet absorbers, adsorbents, sustained-release bodies, liquid-absorbent Agents, ceramic raw materials, various carriers, filter agents, filter aids, microbial cultivation, biological materials, desiccants, fragrances, other carriers or their raw materials, etc. Also look forward to applications on plastics, rubber, coatings, inks, sealing materials, paper, fibers and films.

As a result of intensive studies, the present inventors discovered petal-shaped porous hydroxyapatite fine particles and a method for producing the same, and completed the present invention based on this finding.

disclosure of invention

That is, the first aspect of the present invention satisfies the following formulas (a) to (g), and has a Ca/P atomic ratio of 1.62 to 1.72, and a petal-shaped porous substance having a chemical formula of Ca ₅ (PO ₄ ) ₃ (OH) Hydroxyapatite microparticles as contents.

(a) 0.2≤dx1≤20(μm)

(b) 1≤α≤5 but α=d50/dx1

(c) 0≤β≤2 but β=(d90-d10)/d50

(d)0.01≤dx2≤1(μm)

(e)95≤ω1≤99

(f)70≤ω2≤95

(g)50≤Sw1≤500

in,

dx1: average particle diameter (μm) of petal-shaped porous hydroxyapatite fine particles measured from electron micrographs.

α: dispersion coefficient

d50: 50% average particle diameter (μm) of the petal-shaped porous hydroxyapatite microparticles measured by a microtrack FPA laser particle size distribution meter.

β: sharpness, the smaller the value of the particle size distribution value, the sharper the particle size distribution.

d90: Cumulative 90% particle size (μm) of petal-shaped porous hydroxyapatite fine particles on the sieve passing side measured by a microtrack FRA laser particle size distribution meter.

d10: Cumulative 10% particle size (μm) of petal-shaped porous hydroxyapatite fine particles on the sieve passing side measured by a microtrack FRA laser particle size distribution meter.

dx2: The average particle diameter (μm) of the pores of the petal-shaped porous hydroxyapatite fine particles obtained from the pore distribution measured by the mercury intrusion porosimetry.

3.1：羟基磷灰石的比重ω1: Measure the apparent specific volume (ml/g) according to the static method of JISK 5101-91 20.1 Pigment Test Method, and calculate the static porosity (%) according to the following formula (h)

3.1: Specific gravity of hydroxyapatite

3.1：羟基磷灰石的比重ω2: Fill 0.5g of the sample into a cylinder with a cross-sectional area of ^2cm2 , pressurize it with a pressure of 30kg/ ^cm2 for 30 seconds, measure its thickness with a caliper, and calculate the value of 30kg/ ^cm2 according to the following formula (i) Pressurized porosity (%)

3.1: Specific gravity of hydroxyapatite

Sw1: BET specific surface area m ² /g measured by nitrogen adsorption method.

The content of the second aspect of the present invention is a method of producing the above-mentioned petal-shaped porous hydroxyapatite microparticles by the following steps, that is, the average particle diameter measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) Calcium carbonate aqueous suspension dispersion of 0.1-5 μm, diluted aqueous solution of phosphoric acid, and/or phosphoric acid with an average particle diameter (μm) of 2-10 μm measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) Calcium dihydrogen aqueous suspension dispersion and/or the average particle size measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation)

The aqueous suspension dispersion of calcium hydrogen phosphate dihydrate with a diameter (μm) of 2 to 10 μm is mixed in water with an atomic ratio of Ca/P of 1.62 to 1.72, mixed under the following mixing conditions, and then aged under the following aging conditions Thereafter, dehydration or drying in a dry atmosphere of 700° C. or lower without dehydration is performed, followed by pulverization to produce the above-mentioned petal-shaped porous hydroxyapatite fine particles.

mixed condition

The solid content concentration of the aqueous suspension dispersion of calcium carbonate 1～15%

Concentration of dilute aqueous solution of phosphoric acid 1～50%

The solid content concentration of the aqueous suspension dispersion of calcium dihydrogen phosphate 2～15%

The solid content concentration of the aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt is 2 to 15%

  Peripheral speed (linear speed) of mixing blades                                                                                                                                                                                

Mixing time 0.1～150 hours

The temperature of the mixed water suspension 0～80℃

The pH of the water suspension of the mixed system is 5～9

  Ripening Conditions

 Ca concentration of the mature system 0.4～5%

The peripheral speed (linear speed) of the aging stirring blade is above 0.5m/s

Aging time 0.1～100 hours

The temperature of the water suspension in the aging system is 20～80℃

The pH of the aqueous suspension of the curing system is 6～9

The best way to practice the invention

Hereinafter, the present invention will be described in detail.

The petal-shaped porous hydroxyapatite particles of the present invention have a Ca/P atomic ratio of 1.62 to 1.72 and a chemical formula of Ca ₅ (PO ₄ ) ₃ (OH) hydroxyapatite, which is characterized in that not only the surface but also the inside It is also composed of pores with a petal-like structure. It is a particle size of a specific particle size, a pore size of a specific particle size, a specific surface area of a specific range, a static porosity of a specific range and a pressurized porosity of a specific range, and has excellent of dispersion.

Petal-shaped porous hydroxyapatite particles are composed of not only the surface but also the inside of petal-like structure pores with a specific particle size, and aggregates of spherical particles, igari-shaped particles, and plate-shaped particles Compared with porous hydroxyapatite composed of fine pores, the specific surface area and porosity are larger. Furthermore, since it is a fine particle having a particle diameter of a specific particle size dispersed well, the above-mentioned excellent physical properties can be maintained, and it can be easily used in various applications. In addition, not only the porosity is high, but also the adsorption and liquid absorption properties are good, and the high porosity is maintained even when left under pressure.

For example, various useful substances can be held in the petal-shaped pore space, and on the contrary, harmful and useless substances can also be captured and removed. Further, if necessary, the petal-shaped porous hydroxyapatite fine particles of the present invention can be press-molded to obtain a porous hydroxyapatite press-molded body having a petaloid structure.

Examples of the field of application of the petal-shaped porous hydroxyapatite microparticles of the present invention include catalyst carriers, pharmaceutical carriers, pesticide carriers, microorganism carriers, organism carriers, peroxide carriers, plant growth agents, olefin absorbers, ultraviolet ray Absorbents, adsorbents, slow-release bodies, liquid absorbents, ceramic raw materials, various carriers, filter agents, filter aids, microbial cultivation, biological materials, desiccants, fragrances, other carriers or their raw materials, etc.

Applications related to plastics, rubber, coatings, inks, sealing materials, papermaking, fibers and films can also be expected.

When used as a filler in plastics, rubber, and paint, it is a fine particle with good dispersibility, and the above-mentioned organic matter enters the petal-shaped pore space, and as a result, the affinity becomes excellent. Plastics, rubber, paints, inks, sealing materials, papermaking, fibers, and film compositions filled with petal-shaped porous hydroxyapatite fine particles can be expected to obtain good physical properties because of the above-mentioned good affinity.

Furthermore, catalyst carriers, pharmaceutical carriers, pesticide carriers, microbial carriers, biological carriers, peroxide carriers, plant growth agents, olefin absorbents, ultraviolet absorbents, and adsorbents using petal-shaped porous hydroxyapatite particles , slow-release agent, liquid absorbent, ceramic raw materials, various carriers, filter agents, filter aids, microbial cultivation, biological materials, desiccants, fragrances, composite compositions with other carriers filled in plastics, rubber, coatings , ink, sealing material, and paper composition, composite effects and/or synergistic effects can be expected.

In the manufacturing process and application fields of plastic fibers and films, it is important to prevent adhesion. The manufacturing process has a stretching process, and in actual use, it is subject to friction and wear. At this time, if the affinity between the plastic and the added inorganic anti-blocking agent deteriorates, the added inorganic anti-blocking agent will detach, causing failure. As a result, the above-mentioned organic matter penetrates into the petal-shaped pore space, not only the affinity is very good, but also it is expected to be useful as an anti-blocking agent because of the stress dispersion effect due to the porous structure.

It is also expected to be useful as a filter agent, a filter aid, and a filler for papermaking because of its high specific surface area and the effect of the petal-shaped pore space.

The Ca/P atomic ratio of the petal-shaped porous hydroxyapatite fine particles is preferably a ratio of 1.62 to 1.72. If it is smaller than 1.62, calcium hydrogen phosphate, calcium dihydrogen phosphate, and octacalcium phosphate etc. will coexist, and if it is larger than 1.72, unreacted CaCO ₃ will remain, and high-purity petal-shaped porous hydroxyapatite cannot be obtained. Stone particles.

The average particle diameter dx1 measured from the electron micrograph of the petal-shaped porous hydroxyapatite fine particles is preferably 0.2 μm or more and 20 μm or less. If the average particle size is small, the external specific surface area of the particle surface is high, which is ideal, but if it is smaller than 0.2 μm, the particles are easy to aggregate because the particles themselves are small, and if they are larger than 20 μm, they are easily broken during processing. Preferably, it may be 0.2 μm or more and 5 μm or less, and most preferably, it may be 0.2 μm or more and 3 μm or less.

Dispersion coefficient α of petal-shaped porous hydroxyapatite microparticles (50% average particle diameter measured by microtrack FRA laser type particle size distribution meter/average particle diameter measured according to electron micrograph), the closer the value is to 1, the more Monodisperse particles are suitable, and the larger the numerical value, the more aggregated the particles are, and it can be 1 or more and 5 or less. If it is larger than 5, the dispersibility deteriorates. Preferably it can be more than 1 and less than 2.

The sharpness β of the petal-shaped porous hydroxyapatite particles (the difference between the cumulative 90% and 10% particle diameters d90 and d10 at the sieve passing side measured by the microtrack FRA laser particle size distribution meter divided by the electron micrograph The value of the measured average particle diameter), the closer the value is to 0, the sharper the particle size distribution and the closer to monodisperse. Can be 0 or more and 2 or less. When it is larger than 2, the dispersibility becomes poor. Preferably, it may be not less than 0 and not more than 0.5.

The average particle diameter dx2 of the pores of the petal-shaped porous hydroxyapatite microparticles obtained from the pore distribution measured by mercury intrusion porosimetry may be 0.01 μm or more and 1 μm or less. If it is smaller than 0.01 μm, when it is used in the application described above, it is easy to adsorb as a result, but it is also easy to release. As a carrier of a sustained-release body, the ability to release the adsorbed substance little by little over a long period of time is poor. Or because the pores are too small, it is difficult to apply porous materials to filter agents, filter aids, etc., and the adsorption and slow release of liquids with high surface tension, substances with poor wetting, high viscosity substances and polymer substances are also difficult. If it is larger than 1 μm, the pores are easily destroyed. Preferably, it may be not less than 0.02 μm and not more than 0.5 μm.

The porosity ω1 (%) obtained by the following method of the petal-shaped porous hydroxyapatite fine particles is better, and may be 95% or more and 99% or less. If it is lower than 95%, it cannot be said to be a high void ratio. If it is higher than 99%, handling and handling during storage and transportation become difficult.

3.1：羟基磷灰石的比重ω1: Measure the apparent specific volume (ml/g) of the standing method according to JISK 5101-91 20.1 Pigment Test Method, and calculate the static porosity (%) according to the following formula (h)

3.1: Specific gravity of hydroxyapatite

The higher the pressurized porosity ω2 (%) obtained by the following method of petal-shaped porous hydroxyapatite fine particles is, the better it is, and it can be 70% or more and 95% or less. If it is lower than 70%, the difference from the static porosity ω1 is large, and the porosity tends to decrease during pressurization, and if it is higher than 95%, not only the preparation is difficult, but also the press formability becomes weak.

3.1：羟基磷灰石的比重ω2: Fill a cylinder with a cross-sectional area of 2 cm ² with 0.5 g of the sample, pressurize it with a pressure of 30 kg/cm ² for 30 seconds, measure its thickness with a caliper, and calculate the pressure of 30 kg/cm ² according to the following formula (i) Porosity (%)

3.1: Specific gravity of hydroxyapatite

When petal-shaped porous hydroxyapatite microparticles are used in the various applications described above, especially various carriers, adsorbents, etc., it is better to have a higher specific surface area Sw1 obtained by the nitrogen adsorption method. The nitrogen adsorption method, Sw1 It may be 50 m ² /g or more and 500 m ² /g or less, preferably 100 m ² /g or more and 450 m 2 /g or less, most preferably 150 ^{m 2 /} g or more and 400 m ² /g or less. If the specific surface area exceeds 500 m ² /g, the carrier cannot control the adsorption and sustained release of substances. Also, below 50 m ² /g, the adsorption performance is insufficient.

The novel petal-shaped porous hydroxyapatite microparticles of the present invention can be prepared by mixing specific calcium carbonate aqueous suspension dispersion and phosphoric acid dilute aqueous solution and/or specific calcium dihydrogen phosphate aqueous suspension dispersion and/or The aqueous suspension dispersion of specific calcium hydrogen phosphate dihydrate is mixed at a specific ratio under specific mixing conditions, aged under specific aging conditions, and then dried by a specific method.

Hereinafter, a method for producing petal-shaped porous hydroxyapatite fine particles will be described in detail.

An aqueous suspension dispersion of calcium carbonate and a diluted aqueous solution of phosphoric acid with an average particle diameter of 0.1 to 5 μm measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) and/or by a particle size distribution analyzer ( Aqueous suspension dispersion of calcium dihydrogen phosphate with an average particle diameter (μm) of 2 to 10 μm measured by SA-CP3 manufactured by Shimadzu Corporation and/or by a particle size distribution analyzer (manufactured by Shimadzu Corporation) The aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt with an average particle diameter (μm) of 2 to 10 μm measured by the manufactured SA-CP3) is in water at a ratio of 1.62 to 1.72 at the atomic ratio of Ca/P in the following manner: Mixing Conditions: After mixing, aging under the following aging conditions, dehydration or drying in a dry atmosphere below 700°C without dehydration, and crushing to produce petal-shaped porous hydroxyapatite particles method.

mixed condition

The solid content concentration of the aqueous suspension dispersion of calcium carbonate 1～15%

Concentration of dilute aqueous solution of phosphoric acid 1～50%

The solid content concentration of the aqueous suspension dispersion of calcium dihydrogen phosphate 2～15%

The solid content concentration of the aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt is 2～15%

  Peripheral speed of mixing blades                                                                                

Mixing time 0.1～150 hours

The temperature of the mixed water suspension 0～80℃

  pH of mixed water suspension 5～9

Ripening conditions

 Ca concentration of the mature system 0.4～5%

  The peripheral speed of the aging mixing blade                                                              

Aging time 0.1～100 hours

The temperature of the water suspension in the aging system is 20～80℃

  pH of the aqueous suspension of the aging system                      

The particle size distribution measuring method of the aqueous suspension liquid dispersion of calcium carbonate in the present invention is to measure and calculate with following main points.

Particle size distribution analyzer: SA-CP3 manufactured by Shimadzu Corporation

Sample preparation: drop the sample aqueous suspension dispersion into the following solvent at 25°C as

Specimen for determination of particle size distribution.

Solvent: an aqueous solution in which 0.004% by weight of sodium polyacrylate was dissolved in ion-exchanged water.

Pre-dispersion: Using BRANSON 1200 (manufactured by ャマト), ultrasonically disperse for 100 seconds.

Measuring temperature: 20℃±2.5℃

The average particle diameter measured by a particle size distribution analyzer (manufactured by Shimadzu Corporation SA-CP3) of calcium carbonate aqueous suspension dispersion is preferably small, and may be 0.1 to 5 μm. If it is smaller than 0.1 μm, it will be difficult to prepare, and if it exceeds 5 μm, not only OCP (octacalcium phosphate) which is calcium phosphate other than hydroxyapatite will easily occur, but also the porosity and specific surface area will tend to decrease. Calcium carbonate in the calcium carbonate aqueous suspension dispersion, if meet above-mentioned particle size requirement, heavy calcium carbonate (heavy calcium carbonate karsium) and synthetic calcium carbonate which kind of all can, but, utilize wet synthetic method to manufacture, according to electron The average particle diameter measured by microscopic photographs is suitably 0.01 to 0.2 μm, and the average particle diameter measured by the above-mentioned electron microscopic photographs is preferably 0.01 to 0.07 μm.

As the manufacturing method of the calcium carbonate aqueous suspension dispersion, one or two methods selected from stirring, standing, washing, ultrasonic dispersion, wet pulverization using a medium, and impact non-media wet dispersion can be mentioned. As a suitable method, the "preparation method of a calcium carbonate dispersion" in Unexamined-Japanese-Patent No. 5-319815 is mentioned.

Utilize the average particle diameter measured by the particle size distribution analyzer of the calcium carbonate aqueous suspension dispersion to be 0.1 to 1 μm, and it is better to use the particle size distribution analyzer to measure the cumulative % of particles above 5 μm, preferably 0%.

Calcium carbonate in the calcium carbonate aqueous suspension dispersion also can be any one crystallization system in calcite, aragonite and vaterite, and its particle shape can be spherical, cycol shape (cube), spindle shape, acicular shape and flake shape any of the.

The solid content concentration of the calcium carbonate aqueous suspension dispersion can be 1-15%. Even if it is less than 1%, it can be produced, but there are economical problems such as requiring a large amount of water or increasing the size of the container. If it exceeds 15%, the viscosity of the mixed liquid increases at the end of the mixing or during the mixing, resulting in insufficient stirring. Preferably it is 3-10%. The viscosity of the calcium carbonate aqueous suspension dispersion is high, and when stirring is not sufficient, the mixing is likely to be uneven, so it is preferably diluted with water, and the viscosity is preferably below 20 poises, more preferably below 5 poises.

The concentration of the diluted aqueous solution of phosphoric acid can be 1-50%. It can be produced even if it is less than 1%, but there are economical problems such as requiring a large amount of water or increasing the size of the container. If it exceeds 50%, it becomes partially acidic during mixing, and acidic calcium phosphate other than hydroxyapatite is formed, or the inside of the reaction system becomes inhomogeneous. Preferably 2 to 20%.

The average particle size measured by a particle size distribution measuring device (SA-CP3 manufactured by Shimadzu Corporation) of the calcium dihydrogen phosphate aqueous suspension dispersion is suitable, and may be 2 to 10 μm. Smaller than 2 μm, there are many extremely fine particles, and hydroxyapatite that is easy to produce extremely fine particles, if it exceeds 10 μm, not only calcium phosphate OCP (octacalcium phosphate) other than hydroxyapatite is easy to produce, but also has porosity and ratio Tendency to reduce surface area. It is preferably 2 to 5 µm.

The solid content concentration of the calcium dihydrogen phosphate aqueous suspension dispersion can be 2-15%. Even if it is less than 2%, it can be produced, but there are uneconomical problems such as requiring a large amount of water or increasing the size of the container. If it exceeds 15%, OCP which is calcium phosphate other than hydroxyapatite is likely to occur. Preferably it is 3-10%.

The average particle size measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) of an aqueous suspension dispersion of calcium hydrogen phosphate dihydrate is suitable, and may be 2 to 10 μm. Smaller than 2 μm, there are many extremely fine particles, and hydroxyapatite with extremely fine particles is easy to produce. If it exceeds 10 μm, it is not only easy to produce calcium phosphate OCP (calcium phosphate) other than hydroxyapatite, but also has porosity and ratio. Tendency to reduce surface area. It is preferably 2 to 5 µm.

The solid content concentration of the aqueous suspension dispersion of calcium hydrogen phosphate dihydrate can be 2-15%. Even if it is less than 2%, it can be produced, but there are uneconomical problems such as requiring a large amount of water or increasing the size of the container. If it exceeds 15%, OCP which is calcium phosphate other than hydroxyapatite is likely to occur. Preferably it is 3-10%.

Mixing method, if it is a mixing method that meets the mixing conditions, it is not particularly limited, but preferably under specific mixing conditions, for a specific calcium carbonate aqueous suspension dispersion, under stirring, the diluted aqueous solution of phosphoric acid and It is preferable to slowly drop and mix the specific aqueous suspension dispersion of calcium dihydrogen phosphate and/or the specific aqueous suspension dispersion of calcium hydrogen phosphate dihydrate. For the specific aqueous suspension dispersion of calcium carbonate, it is better to slowly drop the diluted aqueous solution of phosphoric acid into the mixture under stirring.

If the mixing ratio of Ca/P is less than 1.62, calcium phosphate other than hydroxyapatite will be mixed, and if it is greater than 1.72, unreacted CaCO ₃ will remain, and high-purity petal-shaped pores cannot be obtained. hydroxyapatite particles.

The faster the peripheral speed of the mixing blade is, the smaller the particle size of the petal-shaped porous apatite particles generated tends to be, it can be more than 0.5m/s, more preferably more than 3m/s, more preferably 6m/s Above, preferably 6-10m/s. If it is more than 10 m/s, a large amount of energy is required for stirring, and the generated particles tend to be inconsistent, so it is not suitable. When it is less than 0.5 m/s, the stirring is insufficient and the reaction is not uniform.

The mixing time may be 0.1 to 150 hours. If it is less than 0.1 hours, the mixing is insufficient, and if it exceeds 150 hours, it is uneconomical and the specific surface area tends to decrease. It is preferably from 0.3 to 100 hours, most preferably from 2 to 48 hours.

The mixing is stopped halfway, and intermediate aging or resting can also be carried out. Even when the addition is stopped, the higher the liquid temperature, the more the specific surface area tends to decrease, so it is better to be 50°C or lower, more preferably 35°C or lower. In addition, the stop period is preferably within 48 hours, preferably below 35°C, and preferably within 48 hours.

The temperature of the mixed aqueous suspension can be 0-80°C. Below 0°C, the mixed aqueous suspension is easy to freeze and difficult to cool. If it exceeds 80°C, not only a lot of energy is required for heating and heat preservation, but also OCP which is calcium phosphate other than hydroxyapatite tends to be generated, and the specific surface area tends to decrease. Preferably, it may be 10-60 degreeC, Most preferably, it may be 10-35 degreeC.

The set pH of the aqueous suspension at the end of mixing may be 5.0 to 9.0. If the pH of the aqueous suspension is less than 5.0, acidic calcium phosphate other than hydroxyapatite is likely to be generated during subsequent aging. On the other hand, if the pH exceeds 9.0, the crystal growth of hydroxyapatite slows down during subsequent aging and takes a long time. Preferably the pH is 6-8.

By keeping the pH at the time of mixing the phosphoric acid constant, the particle diameter of the petal-shaped porous hydroxyapatite fine particles to be produced can be controlled. That is, the higher the pH of the mixed system is set, the easier it is to form fine particles with a smaller particle size. In addition, the more the pH of the mixed system is kept constant, the easier it is to form monodisperse fine particles.

After the mixing is completed, the curing is carried out under specific curing conditions. Ripening is performed to complete the synthesis of hydroxyapatite and to grow and/or stabilize the petal-like structures.

The Ca concentration of the aging system may be 0.4 to 5%. Even if it is less than 0.4%, it can be produced, but there are uneconomical problems such as requiring a large amount of water or increasing the size of the container. If it exceeds 5%, the viscosity of the mixture will increase at the end of aging or during mixing, and the stirring will become insufficient. .

The temperature of the aging water suspension can be 20-80°C. When it is less than 20°C, the curing time becomes longer, and if it exceeds 80°C, not only a lot of energy is required, but also the specific surface area decreases. Preferably, it is 25-60 degreeC, Most preferably, it is 25-40 degreeC.

The aging time may be 0.1 to 100 hours. When it is less than 0.1 hour, the aging is insufficient, and free ions still exist in the system, and the synthesis of hydroxyapatite is incomplete. If it exceeds 100 hours, it is not economical, and the specific surface area tends to decrease. Preferably it is 1 to 48 hours.

The peripheral speed of the aging stirring blade is 1 m/s or more, more preferably 3 m/s or more, most preferably 6 m/s or more. Uniformity in the system during aging is important, and when it is less than 1 m/s, the uniformity will be significantly reduced, which is not suitable.

The pH of the aqueous suspension at the end of aging can be 5-9. When it is less than 5, acidic calcium phosphate other than hydroxyapatite tends to remain, and when it exceeds 9, unreacted calcium carbonate remains. Preferably 7-8.5.

Drying is carried out after aging, but since heating during drying tends to reduce the specific surface area, it is preferable to dry for a short time.

Although it is satisfactory to improve the drying efficiency by dehydration and washing (including concentration), the processability caused by dehydration becomes poor, and the average thickness of the dry material layer during drying or the average particle size of the dry material block The diameter becomes larger, which is unfavorable, so the dehydration ratio or concentration ratio can be determined by matching the drying device.

Furthermore, it is satisfactory that the average thickness of the dry material layer or the average particle size of the dry material lumps during drying is 10000 μm or less, preferably 1000 μm or less.

And the drying time of the dry powder at 200°C for 2 hours when the heat loss is reduced to less than 10% is as short as possible, preferably 1 to 120 seconds, more preferably 1 to 40 seconds, most preferably 1 ~10 seconds.

Furthermore, as for the drier, hot air conveying type drier such as spray drier and air flow drier is easy to satisfy the above-mentioned suitable conditions, so it is suitable.

As a method of improving drying efficiency, during dehydration (including concentration), it is possible to use a mixed solution of one or more selected from lower monohydric alcohols such as methanol and ethanol, and lower alkyl ethers such as diethyl ether to wash and clean. / or can also be added.

Furthermore, the cleaning solution (filtrate) formed after use is distilled and refined, and the active ingredient can be reused. The amount used may be a solution amount of 5 to 1000% relative to the water content of the aged suspension or dehydrated material block.

If it is less than 5%, there is no effect of improving the drying efficiency, and it is not suitable. If it is more than 1000%, the treatment of the cleaning liquid (filtrate) is complicated, and it is not suitable. It is preferably from 10 to 500%, most preferably from 20 to 300%.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

The following shows the aqueous suspension dispersions A1 to A5 of calcium carbonate used in the examples and comparative examples, the aqueous suspensions B1 to B3 of calcium carbonate, the aqueous suspension dispersion C1 of calcium hydrogen phosphate dihydrate, the diphosphate dihydrate The preparation method of the aqueous suspension dispersion C2 of calcium hydrogen phosphate dihydrate and the aqueous suspension D1 and D2 of calcium hydrogen phosphate dihydrate.

Aqueous Suspension Dispersion A1 of Calcium Carbonate

In 7000 liters of milk of lime (aqueous suspension of calcium hydroxide) with a specific gravity of 1.055 and a temperature of 8° C., a furnace gas with a carbon dioxide concentration of 27% by weight was passed at a flow rate of 24 m ³ to carry out the carbonation reaction to pH 9, and thereafter Stir and ripen at 40-50°C for 5 hours to dissolve the alkali between the particles and disperse to pH 10.8 to prepare calcium carbonate aqueous suspension dispersion A1.

Aqueous suspension dispersion of calcium carbonate A2

In 7000 liters of lime milk with a specific gravity of 1.055 and a temperature of 8°C, a furnace gas with a carbon dioxide concentration of 27% by weight is conducted at a flow rate of ^24m3 , and the carbonation reaction is carried out to a pH of 6.5, and an aqueous suspension dispersion of calcium carbonate is prepared. A2.

Aqueous suspension dispersion of calcium carbonate A3

Dehydrate the calcium carbonate water suspension dispersion A2 with a filter press, dry it with a stirring dryer, and then pulverize it with a pulverizer to form a powder, add water to the powder and mix it, and then mix it in a TK homomixer (5000r/min, 15 minutes), stirring and dispersing to form an aqueous suspension of calcium carbonate with a solid content concentration of 25%, using a wet pulverizer Dyno-MilPyrot type that fills 80% of the glass beads with an average particle diameter of 0.8mm (manufactured by WAB Corporation) was wet pulverized to prepare an aqueous suspension dispersion A3 of calcium carbonate.

Aqueous suspension dispersion of calcium carbonate A4

By conducting carbon dioxide in the aqueous suspension dispersion A1 of calcium carbonate, while adjusting the pH to 10.0-10.8, stirring and aging at 50-60°C for 24 hours, the original particle diameter is prepared to be dispersed in the aqueous suspension of calcium carbonate. Large calcium carbonate aqueous suspension dispersion A4 of body A1.

Aqueous suspension dispersion of calcium carbonate A5

After adding water and mixing the heavy calcium carbonate "Super SSS" (heavy carbonic acid カルシウム "スパパーSSS") (1.2m ² /g) manufactured by Maruo Calcium Co., Ltd., in a TK homomixer (5000r/ min, 15 minutes), stirring and dispersing in 15 minutes), it is modulated into the water suspension dispersion A5 of calcium carbonate whose solid content concentration is 25%.

Table 1 shows the physical properties of the aqueous suspension dispersions A1 to A5 of calcium carbonate.

Table 1 Aqueous suspension dispersion of calcium carbonate According to the average particle size μm measured by the electron microscope photograph The average particle size μm measured by the particle size distribution The cumulative % above 5 μm measured by the particle size distribution A1 A2 A3 A4 A50.05 0.05 0.05 0.10 3.00.48 4.28 0.30 0.75 3.40.0 15.1 0.0 0.0 32.9

Aqueous suspension of calcium carbonate B1

Water was added and mixed with heavy calcium carbonate "R heavy carbon" (0.3 m ² /g) manufactured by Maruo Calcium Co., Ltd. to prepare an aqueous suspension B1 of calcium carbonate having a solid content concentration of 25%.

The particle size distribution is determined in a multimodal manner using natural precipitation.

Aqueous suspension of calcium carbonate B2

Water was added to Wako Pure Chemical Industries Co., Ltd. reagent special grade "calcium carbonate (sedimentation system)" and mixed to prepare an aqueous suspension B2 of calcium carbonate with a solid content concentration of 25%.

Aqueous suspension of calcium carbonate B3

Add water and mix with colloidal calcium carbonate "Korokalso-1" manufactured by Shiraishi Industry Co., Ltd. to prepare an aqueous suspension B3 of calcium carbonate with a solid content concentration of 25%.

Table 2 shows the physical properties of the aqueous suspensions B1 to B3 of calcium carbonate.

Table 2 Aqueous suspension of calcium carbonate Cumulative % above 5 μm by mean particle size μm measured by electron micrographs by particle size distribution B1 B2 B315.0 4.5 0.0724.89 6.42 5.9193.7 73.4 55.2

Aqueous suspension dispersion C1 of calcium hydrogen phosphate dihydrate salt

Prepare a solid by pulverizing "calcium hydrogen phosphate dihydrate" manufactured by Taihei Chemical Industry Co., Ltd. with a pulverizer, adjusting the particle size, adding water and mixing, stirring and dispersing in a TK homomixer (5000r/min, 15 minutes) Aqueous suspension dispersion C1 of calcium hydrogen phosphate dihydrate salt at a content concentration of 25%.

Calcium dihydrogen phosphate aqueous suspension dispersion C2

Taihei Chemical Industry Co., Ltd.'s "calcium dihydrogen phosphate" was pulverized with a pulverizer to adjust the particle size, mixed with water, and stirred and dispersed in a TK homomixer (5000r/min, 15 minutes) to adjust the solid content concentration. Dispersion C2 is an aqueous suspension of 25% calcium dihydrogen phosphate.

Aqueous suspension dispersion D1 of calcium hydrogen phosphate dihydrate salt

Add water to Taihei Chemical Industry Co., Ltd. "calcium hydrogen phosphate dihydrate" and mix, then stir and disperse in a TK homomixer (5000r/min, 15 minutes) to form hydrogen phosphate with a solid content concentration of 25% The aqueous suspension of calcium dihydrate salt was wet-milled using a wet mill Dino-Mil Pylot type (manufactured by WAB Corporation) filled with 80% of glass beads with an average particle diameter of 0.8 mm, and prepared into water of calcium hydrogen phosphate dihydrate salt. Suspension Dispersion D1.

Aqueous suspension dispersion D2 of calcium hydrogen phosphate dihydrate salt

Water was added to "calcium hydrogen phosphate dihydrate" manufactured by Taihei Chemical Industry Co., Ltd. and mixed to prepare an aqueous suspension dispersion D2 of calcium hydrogen phosphate dihydrate having a solid content concentration of 25%.

Table 3 shows the physical properties of the aqueous suspension dispersion C1 of calcium hydrogen phosphate dihydrate, the aqueous suspension dispersion C2 of calcium hydrogen phosphate dihydrate, and the aqueous suspension dispersions D1 and D2 of calcium hydrogen phosphate dihydrate.

table 3 Aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt Aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt Aqueous suspension dispersion of calcium hydrogen phosphate dihydrate salt Average particle size μm measured by particle size distribution C1 D1C2D27.5 8.2 1.5 21.0

Examples 1-15

According to the raw materials and mixing conditions recorded in Tables 4 to 6, a ^0.4m3 stainless steel tank with a diameter of 0.6m turbine blade agitator is placed in a stainless steel tank with a baffle plate, which has been adjusted for concentration dilution and temperature adjustment. Calcium carbonate aqueous suspension dispersion, under stirring, drop and mix the aqueous suspension dispersion of phosphoric acid dilute aqueous solution and/or calcium hydrogen phosphate dihydrate in the ratio of 1.67 with the atomic ratio of Ca/P, form Table 4 The pH of the mixed aqueous suspension at the end of the mixing described in ~ 6, after the completion of the mixing, according to the aging conditions described in Tables 4 to 6, aging while stirring. After the aging, the stirring was stopped, and the supernatant was removed by decantation method (Decante-Sion method), concentrated to a solid content concentration of 8%, and spray-dried to prepare particles E1-E15. In addition, the total weight of a raw material and water is 400 kg. The spray drying conditions are that the particle diameter during spraying is about 0.1mm, the hot air temperature at the inlet is 250°C, the drying time is about 10 seconds, and the heat loss of the dried product immediately after drying is 5-8% at 200°C and 2 hours.

The physical properties of the particles E1 to E15 prepared in Examples 1 to 15 are shown in Tables 9 to 11, and the substances identified by X-ray diffraction are described in descending order of content with the abbreviations described below. Abbreviation Chemical formula JCPDS No. Name HAP: Ca ₅ (PO ₄ ) ₃ (OH) 9～432 Hydroxyapatite TCP: Ca ₃ (PO ₄ ) ₂ XH ₂ O 18～303 Tricalcium phosphate hydrate OCP: Ca ₈ (PO ₄ ) ₆ 5H ₂ O 26～1056 octacalcium phosphate DCPD: CaHPO ₄ 2H ₂ O 9～77 calcium hydrogen phosphate dihydrate CaCO ₃ : CaCO ₃ 5～586 calcite (calcium carbonate)

In addition, the atomic ratio of Ca/P is 1.62 to 1.72, and the chemical formula according to X-ray diffraction is Ca ₅ (PO ₄ ) ₃ (OH) is hydroxyapatite. From the electron microscope photo, not only the surface but also the interior has petals. pore structure, and it is a novel petal-shaped porous substance with a specific particle size, a specific pore size, a specific surface area, a specific range of static porosity, and a specific range of pressurized porosity. Hydroxyapatite particles.

Example 16

It was produced in the same manner as in Example 1 until aging was completed. After the aging is completed, dehydrate with a centrifugal dehydrator to form a dehydrated block, crush the dehydrated block with a compound mixer (Dabul Miki) to form a dehydrated block, dry it with a particle dryer, and then crush it with a pulverizer. Modulated into particle E16. The drying conditions of the particle dryer are: the particle size of the dehydrated block is 10-100mm, the hot air temperature at the inlet is 250°C, the drying time is about 20 seconds, and the heat loss of the dried product immediately after drying is 6% at 200°C and 2 hours . Table 11 shows the properties of the particles E16 prepared in Example 16. Particle E16 obtained in Example 16 has slightly lower specific surface area and static porosity than particle E1 obtained in Example 1, and is a novel petal-shaped porous hydroxyapatite fine particle similar to E1.

Example 17

It was produced in the same manner as in Example 1 until the aging was completed. After the aging was completed, it was dehydrated with a centrifugal dehydrator to form a dehydrated block. After the dehydrated block was dried in a box-type hot air dryer, it was pulverized with a pulverizer to prepare particles E17 . The drying conditions are that the particle size of the dehydrated block is 10-100mm, the drying temperature is 100°C, the drying time is about 20 hours, and the heat loss of the dried product immediately after drying is 6% at 200°C and 2 hours. Table 11 shows the properties of the particles E17 prepared in Example 17. Particles E17 obtained in Example 17 are lower in specific surface area and static porosity than particles E1 obtained in Example 1, but are novel petal-shaped porous hydroxyapatite fine particles similar to E1.

Example 18

Carry out the same production as in Example 1 until the ripening is finished. After the ripening is finished, stop stirring, remove the supernatant by decanting, concentrate to a solid content concentration of 8%, and add 100% of the water content of the concentrated slurry. Methanol was spray-dried to prepare particles E18. In addition, the total amount of raw material, water, and methanol was 400 kg.

The spray-drying conditions are that the particle diameter during spraying is about 0.1mm, the hot air temperature at the inlet is 250°C, the drying time is about 10 seconds, and the heat loss of the dried product immediately after drying is 2-8% at 200°C and 2 hours. Methanol recovered during spray drying is purified by an appropriate method before being reused. Table 11 shows the physical properties of the particles E18 prepared in Example 18. The particle E18 obtained in Example 18 is the same novel petal-shaped porous hydroxyapatite fine particle as the particle E1 obtained in Example 1, and has higher specific surface area and static porosity than E1.

Example 19

Carry out the same manufacture as Example 1 to ripening, after ripening, carry out dehydration with centrifugal dehydrator, form dehydration piece, with respect to the water content of this dehydration piece, carry out dehydration washing with the methanol of relative 50% amount, use The compound mixer crushed the methanol-dehydrated lumps to form dehydrated lumps, which were dried with a particle drier and pulverized with a pulverizer to prepare particles E19. The drying conditions of the particle dryer are: the particle size of the dehydrated block is 10-100mm, the hot air temperature at the inlet is 250°C, the drying time is about 20 seconds, and the heat loss of the dried product immediately after drying is 5% at 200°C for 2 hours . Table 11 shows the physical properties of the particles E19 prepared in Example 19. The particle E19 obtained in Example 19 is the same novel petal-shaped porous hydroxyapatite fine particle as E1, and has a higher specific surface area and static porosity than the particle E1 obtained in Example 1.

Example 20

Carry out to ripening and make in the same way as Example 1, after ripening, carry out dehydration with centrifugal dehydrator, form dehydration piece, with respect to the water content of this dehydration piece, carry out dehydration washing with the methanol of relative 50% amount, in After drying in a box-type hot air drier, it was pulverized with a micro pulverizer to prepare granule E20. The drying conditions are: the particle size of the dehydrated block is 10-100mm, the drying temperature is 100°C, the drying time is about 10 hours, and the heat loss of the dried product immediately after drying is 3% at 200°C and 2 hours. Table 11 shows the physical properties of the particles E20 prepared in Example 20. The particle E20 obtained in Example 20 is the same novel petal-shaped porous hydroxyapatite fine particle as E1, and has higher specific surface area and static porosity than the particle E1 obtained in Example 1.

Table 4 Example 1 2 3 4 5 Types of calcium carbonate aqueous suspension dispersion Prepared calcium carbonate aqueous suspension dispersion Solid content concentration % Solid content concentration % of diluted aqueous solution of phosphoric acid Mixing time h Mixing system Water suspension temperature °C Mixing system water suspension Peripheral speed of stirring blade in pH mixing system m/s Calcium concentration in aging system % aging time h Water suspension temperature in aging system °C Water suspension pH in aging system Peripheral speed of stirring blade in aging system m/s A1 A2 A3 A4 A58 8 8 8 85 5 5 5 52.5 2.5 2.5 2.5 7227 27 27 27 355.5-6 5.5-6 5.5-6 5.5-6 5.5-61.0 1.0 1.0 1.0 1.01.7 1.7 1.7 482 1.7 4 8 1.7 27 27 506.5-8 6.5-8 6.5-8 6.5-8 6.5-81.0 1.0 1.0 1.0 1.0

table 5 Example 6 7 8 9 10 Types of calcium carbonate aqueous suspension dispersion Solid content concentration of calcium carbonate aqueous suspension dispersion % Solid content concentration % of dilute phosphoric acid aqueous solution Mixing time h Mixing system Water suspension temperature °C Mixing system Water suspension pH Mixing Circumferential speed of the stirring blade in the curing system m/s Calcium concentration in the curing system % curing time h temperature of the aqueous suspension in the curing system °C pH of the water suspension in the curing system Peripheral speed of the stirring blade in the curing system m/s A1 A3 A3 A1 A112 8 830 5 5 52.5 2.5 2.5 0.527 27 27 27 705.5-6.5-7 5.5-6 5.61.0 3.0 1.03.9 1.7 1.7 1.7472 3627 27 27 27 50 276.5-8 7.5-8 7.5-8 7.8 7.8 1.0 3.0 6.0 1.0 1.0

Table 6 Example 11 12 13 14 15 The type of aqueous suspension dispersion of calcium carbonate The solid content concentration of the aqueous suspension dispersion of calcium carbonate % The solid content concentration of the diluted aqueous solution of phosphoric acid % The type of aqueous suspension dispersion of calcium hydrogen phosphate dihydrate Water salt aqueous suspension dispersion solid content concentration % calcium dihydrogen phosphate aqueous suspension dispersion type calcium dihydrogen phosphate aqueous suspension dispersion solid content concentration % mixing time h mixing system water suspension temperature °C mixing system water Peripheral speed of stirring blade in suspension pH mixing system m/s Calcium concentration in aging system % aging time h aging system Water suspension temperature °C Water suspension pH at the end of aging The peripheral speed of stirring blade in aging system m/s A1 A1 A1 A1 A18 8 8 8 125C1 C1 C15.5 5.5 5.5C2 C25.5 5.548 48 48 12 1235 15 15 15 156.5-6 7.5-7 7.5-7 7-8 7-81.0 6.0 6.0 1.0 6.07 1.7 7 1. 1.7 1.848 48 48 48 4835 35 35 50 357-7.5 7-7.5 7-7.5 7.5-8 7.5-81.0 6.0 6.0 1.0 6.0

Table 9 Example 1 2 3 4 5 6 7 Corresponding particle*1 E1 E2 E3 E4 E5 E6 E7 d×1 μmαβd×2 μmω1ω2Sw1 component*2 (X-RAY) 7.0 10.0 5.0 4.5 12.0 12.0 2.31.3 2.2 1.3 1.3 1.3 1.2 1.10.9 1.8 0.8 0.9 1.1 1.3 0.70.02 0.02 0.02 0.02 0.03 0.02 0.0297 97 97 96 95 95 9787 85 87 82 72 72 87170 130 200 150 90 95 180HAP HAP HAP HAP HAP HAP HAP ^* 1... Corresponding to the petal-shaped porous hydroxyapatite microparticles of the examples ^* 2... Table 10 of the substances identified by the abbreviation in the order of the largest content from top to bottom Example 8 9 10 11 12 13 14 Corresponding particle*1 E8 E9 E10 E11 E12 E13 E14 d×1 μmαβd×2 μmω1ω2Sw1 component*2 (X-RAY) 1.5 7.0 7.0 8.3 1.8 1.8 5.81.0 1.3 1.4 1.8 1.6 1.4 1.30.6 0.9 1.3 1.2 0.9 0.9 0.90.02 0.02 0.02 0.02 0.02 0.02 0.0497 96 96 95 95 96 9687 85 86 84 83 84 83180 150 130 150 140 160 140HAP HAP HAP HAP HAP HAP HAP

Table 11 Example 15 16 17 18 19 20 Corresponding particle*1 E15 E16 E17 E18 E19 E20 d×1 μmαβd×2 μmω1ω2Sw1 component (X-RAY) 1.6 6.5 6.8 6.8 6.21.2 1.4 1.3 1.3 1.3 1.31.3 1.2 0.7 0.8 0.80.04 0.02 0.03 0.03 0.03 0.0499 97 97 97 9788 88 87 88150 270 270 283HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP HAP Comparative Examples 1-8

According to the raw materials and preparation conditions recorded in Tables 7 to 8, put the water suspension of calcium carbonate to adjust the dilution concentration and temperature in a stainless steel tank equipped with a baffle plate and a stirrer, and under stirring, drop and mix Ca/ After the mixing is completed, the dilute phosphoric acid aqueous solution or the aqueous suspension dispersion of calcium hydrogen phosphate dihydrate having an atomic ratio of P of 1.67 is aged while stirring. After the aging was completed, particles F1 to F8 were prepared by spray drying. In addition, the total amount of raw material and water was 400 kg.

The physical properties of the particles F1 to F8 prepared in Comparative Examples 1 to 8 are shown in Tables 12 to 13.

From X-ray diffraction, it can be seen that the particles F1 to F8 are calcium hydrogen phosphate dihydrate (abbreviation: DCPD) and/or octacalcium phosphate (abbreviation: OCP) containing a large amount of calcium phosphate compounds other than hydroxyapatite and unreacted carbonic acid. Calcium phosphate-based compound of calcium. From electron micrographs, it is observed that the raw material calcium carbonate has an elongated petal shape on the surface, but there is unreacted calcium carbonate inside. It is considered that the particles F1, F2, F3 and F8 are inferred It is a flaky particle of DCPD with a diameter of 100 μm or more.

The physical properties of the particles F1-8 prepared in Comparative Examples 1-8 were remarkably inferior to those of Examples 1-20, as shown in Tables 12-13.

Comparative Example 9

Accommodate 7.4kg of milk of lime (calcium hydroxide aqueous suspension) of solid content concentration 10% in the reaction vessel of 15 liters that baffle plate is housed, stir the dissolver blade of diameter 10cm with 3000r/min on the one hand, at room temperature (27°C), after slowly adding 1.47 kg of phosphoric acid aqueous solution with a concentration of 40% in 240 minutes, it was aged at 27°C for 24 hours with low-speed stirring, then dehydrated with a laboratory filter press, washed with acetone, and heated at 100°C After drying in a box-type drier, it was pulverized to obtain about 1 kg of particle F9. The physical properties of the particles F9 prepared in Comparative Example 9 are shown in Table 13. From X-ray diffraction, it can be seen that the particles F9 are a mixture of tricalcium phosphate hydrate and hydroxyapatite. From the electron micrograph, it is a superfine particle of 0.02 μm. Microparticles, not hydroxyapatite with a petal-like structure. In addition, particle dispersibility was remarkably poor, and other physical properties were remarkably inferior to those of Examples 1-20.

Table 7 comparative example 1 2 3 4 5 Types of aqueous suspensions of calcium carbonate Solid content concentration of aqueous suspensions of calcium carbonate % Solid content concentration of diluted aqueous solutions of phosphoric acid % Types of aqueous suspensions of calcium hydrogen phosphate dihydrate Salts of aqueous suspensions of calcium hydrogen phosphate dihydrate solid content concentration % mixing time h mixing system water suspension temperature °C mixing system water suspension pH at the end of mixing mixing system stirring blade peripheral speed m/s aging system calcium concentration % aging time h aging system water suspension temperature °C Circumferential speed of the stirring blade in the pH curing system of the water suspension at the end of the curing m/s B1 B2 B3 B2 B212 12 12 8 815 15 15D1 D25.5 5.52.5 2.5 2.5 0.5 0.527 27 27 35 353-4 4-5 4-5 6-7 5-81.0 1.0 1.0 1.0 6.03.4 3.4 3.4 48 1.7 48 48 4827 27 27 50 505-6 5.5-6 6-7 5-8 5-81.0 1.0 1.0 1.0 1.0

Table 8 comparative example 6 7 8 Types of calcium carbonate aqueous suspension Solid content concentration of calcium carbonate aqueous suspension % Solid content concentration of phosphoric acid diluted aqueous solution % Mixing time h Mixing system Water suspension temperature Mixing system Water suspension pH Mixing system stirring at the end of mixing Circumferential speed of blade m/s Calcium concentration of curing system Curing time (h) Temperature of water suspension of curing system pH of water suspension of curing system Peripheral speed of stirring blade m/s B2 B2 B225 12 1275 15 152.5 2.5 0.0535 90 354-5 4.5-6 4.5-50.5 0.5 0.58.2 3.4 3.448 12 4850 90 276-8 6-8 5-71.0 1.0 1.0

Table 12 comparative example 1 2 3 4 5 6 7 Corresponding particle*3 F1 F2 F3 F4 F5 F6 F7 d×1 μmαβd×2 μmω1ω2Sw1 component (X-RAY) 25.0 10.0 9.0 11.0 10.5 10.5 12.01.6 2.3 2.5 2.6 2.7 2.7 2.2 3.7 2.1 3.2 3.40.4 0.2 0.2 0.2 0.2 0.289 93 93 94 9745 68 68 708 123DCPD DCPD DCPD DCPD HAP HAP HAP OCPOCP OCP OCP OCP OCP OCP CaCO ₃ CaCO3 CaCO3 CaCO3 CaCO3 CaCO3 CaCO3 CaCO3 HAPHAP HAP HAP ^* 3...Calcium phosphate-based particles corresponding to the comparative example

Table 13 comparative example 8 9 Corresponding particle*3 F8 F9 d×1 μmαβd×2 μmω1ω2Sw1 component (X-RAY) 11.0 0.022.4 6006.2 5.40.2 Not seen 90 9364 6715 171DCPD TCPOCP HAPCaCO3HAP Application Examples 1~20

Particles E1-E20 of the petal-shaped porous hydroxyapatite microparticles of each 1 g of Examples 1-20 were press-molded at a pressure of 25 kg/cm ² as a columnar carrier with a diameter of 2 cm, in 10% tetrachlorohydrin of naphthalene. After immersing in carbonization solution, gasify carbon tetrachloride to prepare naphthalene (pesticide) adsorption slow-release bodies E1-E20. This sustained-release product was placed in a thermostat at 40° C., and the residual rate of naphthalene was measured over time to investigate its sustained-release properties. Table 14 shows the results. The sustained-release performance of any of Application Comparative Examples 1 to 9 described below was remarkably poor and inferior. Compared with the application of Comparative Examples 1 to 9, it was confirmed that the petal-shaped porous hydroxyapatite microparticles of the present invention are good as sustained-release body carriers.

Table 14 Carrier particles Sustained release body Naphthalene adsorption amount Naphthalene residual amount Sustained release after 15 days After 30 days Evaluation g g g Application example 1 Application example 2 Application example 3 Application example 4 Application example 5 Application example 6 Application example 7 Application example 8 Application example 9 Application example 10 Application example 11 Application example 12 Application example 13 Application example 14 Application example 15 Application example 16 Application example 17 Application example 18 Application example 19 Application example 20 Example 1 E1 0.60 0.30 0.15 Good Example 2 E2 0.52 0.27 0.13 Good Example 3 E3 0.62 0.30 0.14 Good Example 4 E4 0.41 0.20 0.11 Good Example 5 E5 0.23 0.13 0.05 Good Example 6 E6 0.23 0.06 0.14 Good Example 7 E7 0.61 0.30 0.14 Good Example 8 E8 0.61 0.30 0.14 Good Example 9 E9 0.51 0.25 0.13 Good Example 10 E10 0.53 0.26 0.14 Good Example 11 E11 0.53 0.27 0.13 Good Example 32 E12 0.40 0.47 0 0.35 0.12 0.08 Good Example 14 E14 0.54 0.26 0.11 Good Implementation Example 15 E15 0.58 0.26 0.13 Good Example 16 E16 0.51 0.26 0.13 Example 17 E17 0.44 0.23 0.11 0.62 0.49 0.35 Entry 19 E11 0.27 Good Example 20 E20 0.61 0.39 0.26 Good

Application Comparative Examples 1-9

In Application Examples 1 to 20, except that "particles E1 to E20 of the petal-shaped porous hydroxyapatite microparticles of Examples 1 to 20" are changed to "particles F1 to F9 of Comparative Examples 1 to 9", the following is the same Naphthalene-adsorbed sustained-release products F1 to F9 were prepared and prepared, and the sustained-release properties of naphthalene over time were investigated for the sustained-release products, and the results are shown in Table 15.

Table 15 Carrier particles Sustained release body naphthalene adsorption amount Naphthalene residual amount Sustained release after 15 days After 30 days Evaluation g g g Application comparison example 1 Application comparison example 2 Application comparison example 3 Application comparison example 4 Application comparison example 5 Application comparison example 6 Application comparison example 7 Application comparison example 8 Application comparison example 9 Comparative Example 1 F1 0.07 0.02 0 Bad Comparative Example 2 F2 0.13 0.04 0 Bad Comparative Example 3 F3 0.19 0.05 0 Bad Comparative Example 4 F4 0.17 0.05 0 Bad Comparative Example 5 F5 0.16 0.04 0 Bad Comparative Example 6 F6 0.19 0.05 0 Bad Comparative Example 7 F7 0.21 0.05 0 Bad comparative example 8 F8 0.16 0.03 0 Bad comparative example 9 F9 0.18 0.07 0 Bad

Application examples 21-40

Using 10 g of the petal-shaped porous hydroxyapatite microparticles E1 to E20 of Examples 1 to 20 as a carrier, 5 g of a 40% aqueous solution of tannin was sprayed and adsorbed to prepare an adsorption agent that adsorbs 2 g of tannin. An adsorbent of petal-shaped porous hydroxyapatite microparticles E1 to E20 of nic acid. In order to test the deodorizing power of the adsorbent, nitrogen gas was flowed at 500 ml/min from one side of a washing bottle (capacity 300 ml) filled with 150 ml of 10% nitrogen water, and the adsorbent was installed and filled from the outlet on the other side. The column of the column was used to introduce ammonia passing through the column into an aqueous solution of hydrochloric acid at pH 4, and the adsorption time until the adsorption capacity of the adsorbent decreased until the adsorption capacity of the adsorbent was not absorbed, and the time until the pH reached 10 or higher, was investigated to investigate the deodorization. Sustainability. The results are shown in Table 16. Compared with Application Comparative Examples 10 to 18 described later, Application Examples 21 to 40 showed good results, and it was confirmed that the petal-shaped porous hydroxyapatite microparticles of the present invention are good as a deodorant carrier.

Table 16 Carrier particles Adsorbent Adsorption time to pH 10 or higher (minutes) Evaluation Application example 21 Application example 22 Application example 23 Application example 24 Application example 25 Application example 26 Application example 27 Application example 28 Application example 29 Application example 30 Application example 31 Application example 32 Application example 33 Application example 34 Application example 35 Application example 36 Application example 37 Application example 38 Application example 39 Application example 40 Example 1 E1 26 Good Example 2 E2 23 Good Example 3 E3 26 Good Example 4 E4 24 Good Example 5 E5 20 Good Example 6 E6 21 Good Example 7 E7 27 Good Example 8 E8 27 Good Example 9 E9 22 Good Example 10 E10 24 Good Example 11 E11 26 Good Example 12 E12 23 Good Example 13 E13 21 Good Example 14 E14 21 Good Example 15 E15 25 Good Example 16 E16 23 Good Example 17 E17 19 Good Example 18 E18 43 Good Example 19 E19 35 Good Example 20 E20 33 Good

Application Comparative Examples 10-18

In Application Examples 21 to 40, except that "particles E1 to E20 of the petal-shaped porous hydroxyapatite microparticles of Examples 1 to 20" are changed to "particles F1 to F9 of Comparative Examples 1 to 9", the following is the same Table 17 shows the results of producing and preparing adsorbents of tannic acid adsorbing particles F1 to F9, and examining the durability of the deodorizing power.

Table 17 Carrier particles Adsorbent Adsorption time to pH 10 or higher (minutes) Evaluation Application comparison example 10 Application comparison example 11 Application comparison example 12 Application comparison example 13 Application comparison example 14 Application comparison example 15 Application comparison example 16 Application comparison example 17 Application comparison example 18 Comparative Example 1 F1 5 Bad Comparative Example 2 F2 7 Bad Comparative Example 3 F3 9 Bad Comparative Example 4 F4 8 Bad Comparative Example 5 F5 8 Bad Comparative Example 6 F6 11 Normal Comparative Example 7 F7 8 Bad Comparative Example 8 F8 7 Bad Comparative Example 9 F9 13 Normal

Application Examples 41～60

Particles E1-E20 of the petal-shaped porous hydroxyapatite microparticles E1-E20 of Examples ^1-20 were press-molded at a pressure of 25 kg/cm2 each, and impregnated with 5% alkyl hydrochloride as a cylindrical carrier with a diameter of 2 cm. 1 g of polyaminoethylglycine aqueous solution was used to prepare sustained-release bodies of inorganic microparticles E1 to E20 adsorbing alkylpolyaminoethylglycine hydrochloride (mold inhibitor). This slow release body is put in the glass container of 500ml, spreads filter paper on it and places 1 slice of 3cm square bread above, is placed in the dark place of humidity 60%, observes the state of the mold that takes place on the bread as time passes, Table 18 shows the results of investigations on its sustained-release properties and anti-fungal properties. They were good compared to Application Comparative Examples 19 to 27 and Application Examples 41 to 60 described later. It was confirmed that the petal-shaped porous hydroxyapatite microparticles of the present invention are good as a sustained-release carrier and an antifungal agent sustained-release carrier.

Table 18 Carrier particles Sustained-release body Whether mold is produced Sustained-release performance after 30 days After 90 days After 120 days Evaluation Application example 41 Application example 42 Application example 43 Application example 44 Application example 45 Application example 46 Application example 47 Application example 48 Application example 49 Application example 50 Application example 51 Application example 52 Application example 53 Application example 54 Application example 55 Application example 56 Application example 57 Application example 58 Application example 59 Application example 60 Example 1 E1 None None Good Example 2 E2 None None Good Example 3 E3 None None Good Example 4 E4 None None Good Example 5 E5 None None Good Example 6 E6 None None Good Example 7 E7 None None Good Example 8 E8 None None Good Example 9 E9 None None Good Example 10 E10 None None Good Example 11 E11 None None Good Example 12 E12 None None Good Example 13 E13 None None None Good Example 14 E14 None None None Good Example 15 E15 None None None Good Example 16 E16 None None None Good Example 17 E17 None None None Good Example 18 E18 None None None Good Example 19 E19 None No Good Example 20 E20 None None No Good

Applied Comparative Examples 19-27

In Application Examples 41 to 60, except that "particles E1 to E20 of the petal-shaped porous hydroxyapatite microparticles of Examples 1 to 20" were changed to "particles F1 to F9 of Comparative Examples 1 to 9", the following preparations were carried out in the same manner. Table 19 shows the results of preparing sustained-release products of alkylpolyaminoethylglycine hydrochloride (antifungal agent) adsorption particles F1 to F9.

Table 19 Carrier particles Sustained-release body Whether mold is produced Sustained-release performance after 30 days After 90 days After 120 days Evaluation Application comparison example 19 Application comparison example 20 Application comparison example 21 Application comparison example 22 Application comparison example 23 Application comparison example 24 Application comparison example 25 Application comparison example 26 Application comparison example 27 Comparative example 1 F1 With and without defect Comparative example 2 F2 Without defect Comparative example 3 F3 Without defect Comparative example 4 F4 Without defect Comparative example 5 F5 Without defect Comparative example 6 F6 Without defect comparative example 7 F7 Comparative example without defect 8 F8 Comparative example without defect 9 F9 No defect

Application Examples 61～80

0.3 g of the petal-shaped porous hydroxyapatite particles E1 to E20 of Examples 1 to 20 were dispersed in 99.7 g of water using an ultrasonic disperser to prepare 100 g of water dispersions E1 to E20. Fix a No. 1 filter paper (manufactured by Toyo Adabasotec) on a glass decompression stand KGS-47 (manufactured by Toyo Adabasotec, 100-mesh stainless steel support screen, effective filtration area 9.6cm ² ), and water After wetting, 100 g of the dispersions E1 to E20 were filtered under a reduced pressure of 300 mmHg, and 1 g of petal-shaped porous hydroxyapatite fine particles E1 to E20 were precoated on No. 2 filter paper. Carry out the filtration test of 100ml of latex ball dispersion liquid of 0.3 μm of 0.5% concentration on it, by measuring the latex ball concentration of filtrate, measure particle capture performance (the capture efficiency is higher the better, and the closer to 100% the better), The results are shown in Table 20. The results in Table 20 demonstrate that the petal-shaped porous hydroxyapatite fine particles of the present invention are useful as filter aids.

Table 20 Use Particle Filter Aid 0.3μm Latex Filter Aid Ball Filtration Accuracy Evaluation Application example 61 Application example 62 Application example 63 Application example 64 Application example 65 Application example 66 Application example 67 Application example 68 Application example 69 Application example 70 Application example 71 Application example 72 Application example 73 Application example 74 Application example 75 Application example 76 Application example 77 Application example 78 Application example 79 Application example 80 Example 1 E1 95 Good Example 2 E2 92 Good Example 3 E3 96 Good Example 4 E4 92 Good Example 5 E5 90 Good Example 6 E6 90 Good Example 7 E7 96 Good Example 8 E8 98 Good Example 9 E9 91 Good Example 10 E10 91 Good Example 11 E11 93 Good Example 12 E12 92 Good Example 13 E13 91 Good Example 14 E14 90 Good Example 15 E15 97 Good Example 16 E16 92 Good Example 17 E17 91 Good Example 18 E18 98 Good Example 19 E19 96 Good Example 20 E20 97 Good

Application Comparative Examples 28-36

In Application Examples 61 to 80, except that "particles E1 to E20 of the petal-shaped porous hydroxyapatite microparticles of Examples 1 to 20" are changed to "particles F1 to F9 of Comparative Examples 1 to 9", the following is the same It was produced, and the filtration test was carried out, and the characteristics of the filter aid are shown in Table 21.

Table 21 Use Particle Filter Aid 0.3μm Latex Filter Aid Ball Filtration Accuracy Evaluation Application comparison example 28 Application comparison example 29 Application comparison example 30 Application comparison example 31 Application comparison example 32 Application comparison example 33 Application comparison example 34 Application comparison example 35 Application comparison example 36 Comparative Example 1 F1 27 Bad Comparative Example 2 F2 28 Bad Comparative Example 3 F3 32 Bad Comparative Example 4 F4 34 Bad Comparative Example 5 F5 38 Bad Comparative Example 6 F6 45 Bad Comparative Example 7 F7 34 Bad Comparative Example 8 F8 31 Bad Comparative Example 9 F9 50 bad

Industrial Applicability

As mentioned above, the petal-shaped porous hydroxyapatite microparticles of the present invention can be used in catalysts, pharmaceuticals, pesticides, microorganisms, etc. It is useful in a wide range of fields, such as fillers for rubber, paint, and paper, and anti-blocking agents for fibers and films.

In addition, according to the production method of the present invention, petal-shaped porous hydroxyapatite can be produced industrially advantageously.

Claims (27)

1. the atomic ratio that satisfies following formula (a)～(g) and Ca/P is 1.62～1.72, chemical formula is Ca ₅(PO ₄) ₃(OH) fine particles of petaloid porous hydroxyapatite,

(a)0.2≤dx1≤20(μm)，

(b) 1≤α≤5, wherein, α=d50/dx1,

(c) 0≤β≤2, wherein, β=(d90-d10)/d50,

(d)0.01≤dx2≤1(μm)，

(e)95≤ω1≤99，

(f)70≤ω2≤95，

(g)50≤Sw1≤500，

Wherein,

Dx1: according to the fine particles of petaloid porous hydroxyapatite of electron micrograph mensuration

Median size (μ m),

α: dispersion coefficient,

D50: by the fixed petal-shaped porous matter hydroxyl phosphorus of little track FPA laser type size-grade distribution instrumentation

Atomic 50% median size of lime stone (μ m),

β: acutance, by the size-grade distribution value, numerical value is more little, and the distribution of granularity is sharp more,

D90: by the fixed petal-shaped porous matter hydroxyl phosphorus of little track FRA laser type size-grade distribution instrumentation

The atomic screen cloth of lime stone adds up 90% particle diameter (μ m) by side,

D10: by the fixed petal-shaped porous matter hydroxyl phosphorus of little track FRA laser type size-grade distribution instrumentation

The atomic screen cloth of lime stone adds up 10% particle diameter (μ m) by side,

Dx2: the petal-shaped porous matter hydroxyl that distributes and draw by the pore of measuring according to mercury penetration method

The median size of the pore of apatite fine particle (μ m),

ω 1: measure apparent ratio according to the settled process of JISK5101-91 20.1 pigment test method(s)s

Hold (ml/g), leave standstill voidage (%) according to what following formula (h) was calculated,

3.1: the proportion ω 2 of hydroxyapatite: at cross-sectional area 2cm ²Cylinder in fill the 0.5g sample, with 30kg/cm ²Pressure

Power pressurization 30 seconds is measured its thickness with slide calliper rule, calculates according to following formula (i)

30kg/cm ²Pressurization voidage (%)

3.1: the proportion of hydroxyapatite

Sw1: according to the BET specific surface area m of determination of nitrogen adsorption ²/ g.

2. the described fine particles of petaloid porous hydroxyapatite of claim 1, wherein, median size dx1 satisfies following formula (j)

(j)0.2≤dx1≤5(μm)。

3. the described fine particles of petaloid porous hydroxyapatite of claim 1, wherein, median size dx1 satisfies following formula (k)

(k)0.2≤dx1≤3(μm)。

4. each described fine particles of petaloid porous hydroxyapatite in the claim 1～3, wherein, dispersion coefficient α and acutance β satisfy following formula (1) and (m) simultaneously

(l)1≤α≤2(μm)

(m)0≤β≤0.5(μm)。

5. each described fine particles of petaloid porous hydroxyapatite in the claim 1～3, wherein, BET specific surface area Sw1 satisfies following formula (n)

(n)100≤Sw1≤450。

6. the manufacture method of fine particles of petaloid porous hydroxyapatite, it is characterized in that, in water, the median size that to be measured by the particle size distribution device with following mixing condition be the dilute aqueous solution of the calcium carbonate water suspension dispersion of 0.1～5 μ m and phosphoric acid and/or be that the monocalcium phosphate aqeous suspension dispersion of 2～10 μ m and/or the median size measured by the particle size distribution device are the aqeous suspension dispersion of the secondary calcium phosphate two water salt of 2～10 μ m by the median size that the particle size distribution device is measured, be after 1.62～1.72 the mixed with the atomic ratio of Ca/P, carry out slaking with following slaking condition again, dewater then or under not dewatering after carrying out drying under the dry atmosphere below 700 ℃, carry out grinding and processing, mixing condition

The aqeous suspension dispersion solids content concn 1～15% of lime carbonate,

The dilute aqueous solution concentration 1～50% of phosphoric acid,

The aqeous suspension dispersion solids content concn 2～15% of monocalcium phosphate,

The aqeous suspension dispersion solids content concn 2～15% of secondary calcium phosphate two water salt,

Mix more than the circumferential speed 0.5m/s of agitating vane,

Mixing time 0.1～150 hour,

0～80 ℃ of mixed stocker aqeous suspension temperature,

Mixed stocker aqeous suspension pH 5～9, the slaking condition

The Ca concentration 0.4～5% of slaking system,

More than the circumferential speed 0.5m/s of slaking agitating vane,

0.1～100 hour curing time,

Slaking is 20～80 ℃ of aqeous suspension temperature,

Slaking is aqeous suspension pH 6～9.

7. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 6, wherein, calcium carbonate water suspension dispersion with respect to solids content concn 1～15%, under agitation, slowly splash into and the phosphoric acid dilute aqueous solution of melting concn 1～50% and/or be that the monocalcium phosphate aqeous suspension dispersion of 2～10 μ m and/or the median size measured by the particle size distribution device are the aqeous suspension dispersion of the secondary calcium phosphate two water salt of 2～10 μ m by the median size that the particle size distribution device is measured.

8. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 6, wherein, with respect to the aqeous suspension dispersion of the lime carbonate of solids content concn 3～10%, under agitation, slowly splash into and the dilute aqueous solution of the phosphoric acid of melting concn 2～20%.

9. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 6～8, wherein, lime carbonate utilizes the manufacturing of wet type synthesis method, and the median size of measuring according to electron micrograph is 0.01～0.2 μ m.

10. the manufacture method of each described fine particles of petaloid porous hydroxyapatite in the claim 6～8, wherein, lime carbonate utilizes the manufacturing of wet type synthesis method, and the median size of measuring according to electron micrograph is 0.01～0.07 μ m.

11. the manufacture method of each described fine particles of petaloid porous hydroxyapatite in the claim 6～8, wherein, calcium carbonate water suspension dispersion is that the median size of being measured by the particle size distribution device is the calcium carbonate water suspension dispersion of 0.1～1 μ m.

12. the manufacture method of each described fine particles of petaloid porous hydroxyapatite in the claim 6～8, wherein, calcium carbonate water suspension dispersion is that the accumulation % of the oversize particle more than the 5 μ m that measured by the particle size distribution device is 0% calcium carbonate water suspension dispersion.

13. the manufacture method of each described fine particles of petaloid porous hydroxyapatite in the claim 6～8, wherein, mixing condition and slaking condition are as follows: mixing condition

The aqeous suspension dispersion solids content concn 3～10% of lime carbonate,

The dilute aqueous solution concentration 2～20% of phosphoric acid,

Mix more than the circumferential speed 3m/s of agitating vane,

Mixing time 2～48 hours,

10～60 ℃ of mixed stocker aqeous suspension temperature,

Mixed stocker aqeous suspension pH 6～8, the slaking condition

1～48 hour curing time,

Slaking is 25～60 ℃ of aqeous suspension temperature.

14. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 13, wherein, mixing condition and slaking condition are following conditions: mixing condition

Mix more than the circumferential speed 6m/s of agitating vane,

10～35 ℃ of mixed stocker aqeous suspension temperature, the slaking condition

More than the circumferential speed 3m/s of slaking agitating vane,

Slaking is 25～40 ℃ of aqeous suspension temperature,

Slaking is aqeous suspension pH 7～8.5.

15. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 14, wherein, mixing condition and slaking condition are following conditions:

During mixing and the agitating vane circumferential speed during slaking be more than the 6m/s.

16. the manufacture method of each described fine particles of petaloid porous hydroxyapatite in the claim 6～8, wherein, the mean thickness of the dry wood bed of material in drying or the median size of drying material piece are below the 10000 μ m.

17. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 14, wherein, the mean thickness of the dry wood bed of material in drying or the median size of drying material piece are below the 10000 μ m.

18. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 15, wherein, the mean thickness of the dry wood bed of material in drying or the median size of drying material piece are below the 10000 μ m.

19. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 16, wherein, the median size of the mean thickness of the dry wood bed of material or drying material piece is below the 1000 μ m.

20. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 17, wherein, the median size of the mean thickness of the dry wood bed of material or drying material piece is below the 1000 μ m.

21. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 18, wherein, the median size of the mean thickness of the dry wood bed of material or drying material piece is below the 1000 μ m.

22. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 16, wherein, extremely the hot decrement of dry powder under 200 ℃, when heating in 2 hours is that be 1～40 second the time of drying below 10%.

23. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 17, wherein, extremely the hot decrement of dry powder under 200 ℃, when heating in 2 hours is that be 1～40 second the time of drying below 10%.

24. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 18, wherein, extremely the hot decrement of dry powder under 200 ℃, when heating in 2 hours is that be 1～40 second the time of drying below 10%.

25. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 16, wherein, after slaking ends, with respect to moisture amount of moisture, the mixed solution of one or two or more kinds composition selected from low-grade monobasic alcohol class, low alkyl group ethers with 5～1000% is cleaned and/or is added slaking end of a period suspension to maybe in this dehydration piece.

26. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 17, wherein, after slaking ends, with respect to moisture amount of moisture, the mixed solution of one or two or more kinds composition selected from low-grade monobasic alcohol class, low alkyl group ethers with 5～1000% is cleaned and/or is added slaking end of a period suspension to maybe in this dehydration piece.

27. the manufacture method of the described fine particles of petaloid porous hydroxyapatite of claim 18, wherein, after slaking ends, with respect to moisture amount of moisture, the mixed solution of one or two or more kinds composition selected from low-grade monobasic alcohol class, low alkyl group ethers with 5～1000% is cleaned and/or is added slaking end of a period suspension to maybe in this dehydration piece.